The processing of silver halide photographic materials, for example the processing of silver halide color photographic materials comprises generally a color development stage and a desilverization stage. In the desilverization stage, developed silver formed during the course of color development is oxidized by a bleaching agent having an oxidizing effect on a silver salt (bleaching), and the silver salt together with unexposed silver halide is converted into soluble salts using a fixing agent and removed from the light-sensitive layers. Ferric ion complex salts (e.g., iron(III) complex salts of aminopolycarboxylic acids) are mainly used as the bleaching agents, and thiosulfates are usually used as the fixing agents.
Bleaching and fixing can be separately carried out as a bleaching stage and a fixing stage, or bleaching and fixing can be simultaneously carried out as a bleaching-fixing stage. The details of these processing stages are described in James, The Theory of Photographic Process, Fourth Edition (1977).
Generally, the above processing stages are carried out using automatic processors. Particularly, small-size automatic processors called mini-laboratories have been installed in shops, and rapid processing service to customers has spread in recent years. The bleaching agent and the fixing agent are used in the same bath as a bleaching-fixing bath in the processing of color paper because of the miniaturization of the processors and the demand for rapid processing.
Further, the reduction in the replenishment rates of processing solutions has been positively made in the above processing stages from the viewpoints of resource saving and the preservation of the environment. However, when the replenishment rate of developing solution is merely reduced, a problem occurs in that development activity is lowered by the accumulation of matter dissolved out from the light-sensitive materials, particularly the accumulation of iodide ion and bromide ion which are intense development restrainers. As a result, rapid processing is deteriorated. JP-A-58-95345 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"), JP-A-59-232342, JP-A-61-70552 and WO 87-04534 disclose a method using silver halide light-sensitive materials having a high silver chloride content to reduce the accumulation of iodide ion and bromide ion and to thereby achieve rapid processing. This method is considered to be an effective method which allows rapid processing to be carried out even in the case of a low replenishment rate for the developing solutions.
JP-A-4-443 discloses that the dye image has excellent stability, and the reduction in the replenishment rate as well as ultra-high rapid processing can be achieved when silver halide light-sensitive materials having a high silver chloride content are processed with color developing solutions containing hydroxyalkyl-substituted p-phenylenediamine derivatives with a specific structure as color developing agents.
A marked improvement in process rapidity and an improvement in the stability of processing solutions have been required in the bleaching-fixing stage. However, there is the problem that when rapid bleaching-fixing processing is carried out after rapid color development, developing agents (which can be removed in a conventional bleaching-fixing stage) or sensitizing dyes and antihalation dyes used in the light-sensitive materials are not sufficiently removed. As a result, stain is formed on an image after processing, that is, a white area on the image is stained and the image is not good. Accordingly, a processing solution and a processing method which solve the above-described problem have been required.
JP-A-49-84440, JP-A-61-51147, JP-A-62-129854, JP-A-62-135833, JP-A-1-211757 and JP-A-1-213653 disclose that onium salts such as typically quaternary ammonium salts or organic bases of conjugate acids are present as a bleaching accelerator in a bleaching bath to accelerate the desilverization treatment in the processing of conventional silver halide light-sensitive materials containing silver chlorobromide or silver iodobromide. Further, JP-A-1-211757 discloses that bleaching accelerators are useful particularly when reversal color light-sensitive materials containing a high silver content emulsion for photographing and color negative light-sensitive materials containing a high silver content emulsion for photographing are processed.
However, these patent specifications disclose nothing concerning a method for accelerating the rapid removal of developing agents, coloring materials such as sensitizing dyes, other dyes, etc. Further, it has been found that some of these desilverization accelerators do not operate well in rapid processing including the subsequent rinsing stage because the stability of the image is deteriorated when the time of the subsequent rinsing or stabilization stage is shortened.
There is a possibility that the removal of the color developing agents from the light-sensitive materials in the bleaching-fixing bath and the coloring materials such as sensitizing dyes, other dyes, etc. is insufficiently achieved when rapid processing is carried out in the desilverization stage such as in the bleaching-fixing stage and the reduction of the replenishment rate of the processing solution is achieved in this stage to process rapidly photographic materials such as color photographic materials and to simplify the processing thereof. Further, the shorter the time of the subsequent rinsing or stabilization stage, the more the load of removal of undesired materials in the desilverization stage such as the bleaching-fixing stage is increased.
When rapid processing of all of the processing stages is contemplated as mentioned above, the problem with regard to the deterioration (staining) of the white area on the image caused by undesired components left behind in the light-sensitive materials becomes markedly apparent. Particularly, the problem with regard to the removal of the developing agents is serious. When the time of bleaching-fixing is shortened, developing agents are left behind in the light-sensitive materials, and stain tends to be formed on the image. It has been found that a low pH, such as a pH not higher than 5, is favorable in the removal of the developing agents in the bleaching-fixing stage. However, processing over a long period of 20 seconds or longer at a low pH is not preferred because maximum density is reduced. Further, when the pH is extremely low, removal of the dyes and the sensitizing dyes is retarded, and hence extremely low pH is disadvantageous in solving the problem with regard to stain on the image.
Accordingly, sufficient removal of the developing agents, the dyes and the sensitizing dyes in the rapid processing of the photographic materials has been desired. Particularly, development of a processing method capable of sufficiently removing these compounds in the desilverization stage such as the bleaching stage, the fixing stage or the bleaching-fixing stage, has been desired.